Automated flocculation titrimeter system

ABSTRACT

A system for determining parameters and compatibility of a substance such as an asphalt or other petroleum substance uses titration to highly accurately determine one or more flocculation occurrences and is especially applicable to the determination or use of Heithaus parameters and optimal mixing of various asphalt stocks. In a preferred embodiment, automated titration in an oxygen gas exclusive system and further using spectrophotometric analysis (2-8) of solution turbidity is presented. A reversible titration technique enabling in-situ titration measurement of various solution concentrations is also presented.

TECHNICAL FIELD

[0001] This invention relates generally to titration methods andapparatus, and more specifically to automated titration methods andapparatus for accurate determination of Heithaus parameters andresultant accurate prediction of compatability of petroleum residua suchas asphalt.

BACKGROUND

[0002] The Heithaus test, which models asphalt explicitly as a colloidalsystem, was developed in the early 1960's by J. J. Heithaus to studycompatibility characteristics of petroleum residua used in the roofingindustry. Since then, the Heithaus test has found use in the pavingindustry as a method to study rutting propensity and oxidative agehardening. The original method, which suffered from operator dependencyand poor data repeatability, has recently been automated. An automatedHeithaus titration (AHT) test has been developed based on lighttransmitting/scattering detection of the onset of flocculation usingultraviolet (UV)-visible spectrophotometry. The AHT test has been foundto significantly reduce operator dependency and improve datarepeatability, in some cases, by an order of magnitude. As a result ofthe improved repeatability of data, Heithaus parameters are found tomeasure physical properties that relate to rheological properties ofasphalt.

[0003] Historically, asphalts have been classified into gel-typeasphalts and sol-type asphalts. Gel-type asphalts usually arecharacterized by non-Newtonian rheological behavior, relatively lowvariation of viscosity with temperature, and low ductility. Sol-typeasphalts exhibit more Newtonian rheological behavior, are highlytemperature susceptible, and are more ductile. The two classificationsrepresent extremes; most asphalts are of an intermediate nature.Sol-type asphalts have also been designated as compatible asphalts,while gel-type asphalts have been designated as incompatible asphalts.

[0004] The terms “compatible” and “incompatible” (or even sol and gel)arose from what became known as the colloidal model of asphalt structureand often are used as general terms to relate “self-compatibility” and“self-incompatibility”. This model considers asphalts to be dispersionsof what are termed “micelles,” consisting of polar, aromatic moleculesin viscous oils. In the model, the degree to which the so-called“micelles” form extended gel structures (which can be broken up by heatand shear) determines the relative degree of compatibility. In acompatible asphalt, the dispersed materials are believed to be wellpeptized by the solvent, either because the dispersed materials aresmall in amount and/or tend not to form strong associations, and/orbecause the solvent effectively disperses the “micelles.” In anincompatible asphalt, associations of dispersed materials presumably aremore extensive and are not so efficiently peptized by the solvent.

[0005] The colloidal model has been subjected to much criticism inrecent years. The principal objection is that there is no evidence for“micellar” structures, either classical or inverse, in asphalts. Theterm “micelle,” which implies the existence of a separate phase withdistinct boundaries, may in fact be inappropriate. More recently, adifferent microstructural model of asphalt structure had been proposed.Even this has now been refined by the present inventors. In the model,associations of polar, aromatic molecules of varying sizes areconsidered to be dispersed in a solvent moiety composed of less polar,relatively small molecules. No distinct phase boundaries are believed tobe present. Regardless of the validity of the model, though, the conceptof compatibility as a measure of mutual miscibility of differentchemical components of asphalts is still useful. Compatible asphaltsdiffer from incompatible asphalts in their physical properties andtherefore may be expected to behave differently in pavements. Changes inthe degree of compatibility often have opposing effects on importantperformance related properties. For example, a change that may result inbetter rutting resistance may also result in more embrittlementresulting from oxidative age hardening. Thus, compromises incompatibility can be viewed as necessary for optimum overall pavementperformance.

[0006] Asphaltenes are solid materials that precipitate when asphaltsare treated with solvents such as n-pentane, n-hexane, n-heptane,iso-octane, etc. Maltenes are the components of asphalts notprecipitated by the above alkane solvents. Asphaltenes are more aromaticthan maltenes and contain more heteroatoms. Thus intermolecularinteractions are likely more extensive in asphaltenes than in maltenes.This may be reflected in the greater molecular weights of asphaltenescompared with maltenes. In the colloidal model of asphalt structure,asphaltenes are believed to correspond to the dispersed materials andmaltenes to the solvent. Therefore, asphaltenes may be mainlyresponsible for the internal structure of asphalts and may dominate manyphysical properties. Thus the amount of asphaltenes in an asphalt couldbe one measure of compatibility. Compatible asphalts may have smalleramounts of asphaltenes than incompatible asphalts. The ease with whichasphaltenes are dispersed may be dependent on their peptizability and onthe dispersing power of maltenes. Oxidative aging of an asphalt could bepredicted to influence compatibility by formation of polar molecules,which may result in more extensive molecular associations, but also mayresult in a better solvent.

[0007] The best known measurement of compatibility of asphalts thattakes all the above factors into account is the Heithaus test. Heithausobserved that for straight-run asphalts, measuring asphaltene contentsprovided a reasonably good estimate of compatibility. Perhapssurprisingly, in blended asphalts from different sources (compositeasphalts or asphaltic composites), weight-averaging asphaltene contentsdid not provide reliable estimates of compatibility. It thus was viewedas necessary to test each blend and develop a different method that tookinto consideration factors other than asphaltene content. In Heithaus'original “classical” test, solutions of various concentrationscontaining different weights of asphalt (W_(a)) were dissolved in aconstant volume of solvent (V_(S)), e.g., toluene or benzene, weretitrated with normal alkane solvents, including, e.g., n-heptane, untilflocculation (asphaltene precipitation) was observed. Flocculation wasdetected by spotting a drop of the solution onto filter paper, to permitthe resulting phase separation of precipitated material from materialremaining in solution to be observed. This was done by a directobservation or through the use of a microscope. The volume of titrant(V_(T)) required to initiate flocculation in each solution was then usedto determine flocculation ratios (FR), calculated asFR=V_(S)/(V_(S)+V_(T)). Values of flocculation ratios were plottedversus dilution concentration (C), calculated as C=W_(a)/(V_(S)+V_(T))and a best fit straight line connecting the points was extrapolated tothe x- and y-axes. The x and y intercepts determined from theextrapolation, referred to as the dilution concentration minimum(C_(min)) and the flocculation ratio maximum (F_(max)), respectively,were used to calculate three Heithaus parameters, defined below.

[0008] The theoretical significance of the quantity C_(min) was that itrepresented the quantity of titrant (n-heptane for the classical method)that would be just enough to cause asphaltene precipitation in the neatasphalt, undissolved in toluene, assuming it would be possible to do so.FR_(max) represented a measure of the solubility parameter, δ, which maybe measured in Hildebrand units, H, at which asphaltene flocculationoccurred in the asphalt as a whole. Thus, the Heithaus method measuredsome fundamental properties of asphalts and blends that asphalteneconcentration values did not measure.

[0009] In the original “classical” test, the Heithaus parameters were:p_(a)=1−FR_(max), which measured the peptizability of the asphaltenefraction; p_(o)=FR_(max)(C_(min) ⁻¹+1), which measured the solvent powerof the maltene fraction, and p=p_(o)/(1−p_(a)), which measured theoverall compatibility of the asphalt. Larger values of p_(a), p_(o), andP represented peptizable asphaltenes, maltenes that were a good solvent,and a compatible asphalt overall. Smaller values of p_(a), p_(o), and Prepresented the reverse. Interestingly, the p_(a) and p_(o) values didnot necessarily vary directly with one another among asphalts. Anasphalt may be composed of asphaltenes that are not readily peptizable,but which are dispersed in maltenes that have good solventcharacteristics, or the reverse.

DISCLOSURE OF INVENTION

[0010] As alluded to earlier, the original “classical” test can betedious and can yield highly variable results, especially with waxyasphalts. Thus, an improved compatibility test has be long desired. Asthe present inventors recognized, a study of asphaltene flocculationbehavior was needed to develop an improved compatibility test. As aresult, initially a basic automated Heithaus titration procedure wasdeveloped based on methods for determining asphaltene precipitationcharacteristics. That basic procedure has now been refined to make itpractical and commercially valuable.

BRIEF DESCRIPTION OF DRAWINGS

[0011]FIG. 1. The titration portion of one embodiment of the automatedtest apparatus is shown schematically in FIG. 1 with:

[0012] 1. Stir Plate

[0013] 2. Inflow from Circulating Water Bath

[0014] 3. {fraction (1/16)}″ I.D. Tubing

[0015] 4. 0.1 mm Pathlength Quartz Flow Cell (To Be Housed inSpectrophotometer)

[0016] 5. Tube End Fitting Adaptors

[0017] 6. Circulation Pump (High Flow Rate Metering Pump)

[0018] 5 7. Titrant Pump (Low Flow Rate Metering Pump)

[0019] 8. Fitting for {fraction (1/16)}″ I.D. Tubing

[0020] 9. Teflon Cover

[0021] 10. 30-mL Vial

[0022] 11. Neoprene Tubing

[0023] 12. Water-Jacketed Titrant Vessel

[0024] 13. Outflow to Circulating Water Bath

[0025] 14. Water-Jacketed Reaction Vessel

[0026] 15. Stir Plate

[0027]FIG. 2. An alternative design for the titration portion of theautomated test apparatus is also shown schematically in FIG. 2 with:

[0028] 1. FMI Metering Pump

[0029] 2. FMI Dispersing Pump

[0030] 3. Sample Vial with Water Jacket

[0031] 4. Flow Cell with Teflon Couplers

[0032] 5. Cell Holder

[0033] 6. Light Source

[0034] 6a. Fiber Optics Cable

[0035] 7. PC (type) Computer

[0036] 8. UVvis Spectrophotometer

[0037] 9. Titrant Reservoir

[0038] 10. Stirring Plate

[0039]FIG. 3 A possible design with dimensions of one embodiment of thesolution containment element is shown in FIG. 3 with:

[0040] A Top View

[0041] B Profile View

[0042]FIG. 4 A possible design with dimensions for one embodiment of thesolution containment element is shown in FIG. 4 with:

[0043] A Top View

[0044] B Profile View

[0045]FIG. 5FIG. 5 shows representative transmission vs time results forvarious samples: Percent transmittance versus titrant delivery time(flocculation curves) plotted for AAD-1 SHRP core asphalt solutionsprepared at four different concentrations, titrated with iso-octane(titrant flow rate υ_(T)=0.350=0.005 mL/min) with:

[0046] t_(R): Retention Time to Peak Apex

[0047] υ_(T): Titrant Flow Rate

[0048] V_(T)=t_(R)×υ_(T): Volume of Titrant at Flocculation Onset

[0049]FIG. 6FIG. 6 shows a percent transmittance versus titrant deliverytime (flocculation curves) plotted for 7 SHRP core asphalt solutionsprepared as 1.0000=0.0005 g of asphalt dissolved in 1.000=0.005 mL oftoluene, titrated with iso-octane (titrant flow rate υ_(T)=0.350=0.005mL/min)

[0050]FIG. 7 Percent transmittance versus time plotted on a strip chartrecorder for a solution of SHRP core asphalt

[0051] (AAM-1) dissolved in toluene, continuously circulated through aUV-visible spectrophotometric detection

[0052] system as 1.0 mL aliquots of iso-octane are added intermittently.

[0053]FIG. 8 One possible embodiment of AHT w/iso-octane reaction vesselconsisting of a 100 mL (optional or 200 mL water jacket, 30 mL samplevial, and a custom designed Teflon cover/vial holder with:

[0054] 1. H₂O

[0055] 2. Teflon Cover

[0056] 3. Out to Flow Ceil

[0057] 4. In from Titrant

[0058] 5. In from Flow Cell

[0059] 6. {fraction (1/16)}″ ID Viton or Teflon Tubing

[0060] 7. 0.022″ ID Viton or Teflon Tubing

[0061] 8. 30 mL Vial (Screws up into Teflon Cover)

[0062] 9. 200 mL Water Jacket (WJ2)

[0063] 10. H₂O Out

[0064]FIG. 9 One configuration of AHT apparatus with:

[0065] 1. UV Visible Spectrophotometer

[0066] 2. to Flow Cell

[0067] 3. FMI Metering Pump (PI)

[0068] 4. Stir Plate

[0069] 5. from Water Bath/Circulator

[0070] 6. (TR) Titrant Reservoir

[0071] 7. to WJ2

[0072] 8. (P2) FMI Metering Pump

[0073] 9. Viton Tubing

[0074] 10. from TR

[0075] 11. (WJ2) Water Jacket

[0076] 12. to Water Bath/Circulator

[0077] 13. Stir Plate

[0078] 14. Chrontrol Power Switch

[0079] 15. Circuit A

[0080] 16. Circuit B

[0081] 17. Circuit C to Water Bath Power Supply

[0082] 18. Integrator

[0083]FIG. 10—A schematic representation of one embodiment of a flowcell element

[0084]FIG. 11—Reversible Heithaus titration of SHRP core asphalt AAA-1—%Transmittance vs. Time with a Second 1.0 mL Addition of Toluene atapproximately 1000 seconds and a First 1.0 mL Addition of Toluene atapproximately 760 seconds.

[0085]FIG. 12—Sample Graph of an Analyzed Spectrophotometer reading

MODE(S) FOR CARRYING OUT THE INVENTION

[0086] Accordingly, the present invention provides improved andautomated methods to determine various properties of substances such asasphalts in a manner which is practical and commercially valuable. Asmay be understood, the invention discloses methods and apparatus whichmay be combined and utilized in a variety of manners. Importantly, whilesome methods and devices are disclosed, it should be understood that allof these can be varied in a number of ways. Importantly, as to all ofthe foregoing, all of these facets should be understood to beencompassed by this disclosure.

[0087] In one embodiment, the test method may be used to measure thecompatibility or colloidal stability of asphalt and heavy residua, suchas petroleum residua, by determining the flocculation onset, i.e. thepoint at which asphaltenes just begin to precipitate from a solution ofknown weight sample prepared in a “solvent” and titrated with a“non-solvent”, resulting in a change in a solution turbidity, which maybe indicated by a change in transmittance as may be measured by aspectrophotometer, also referred to as a spectrometer. The advantages ofthe automated method are that it can act to monitor asphalt flocculationby observing sharp or more gradual changes in transmittance—such as at740 nm or the like—of the solution being titrated. Such methods can bedesigned so as to not be as operator dependent as the original method.Importantly, the improved automated Heithaus method may now be used forthe testing of not only neat asphalts, but also asphalt blends (e.g.,blends of asphalts from one or more different stocks), and evenoxidatively aged asphalts.

[0088] In order to understand the improvements now disclosed, it may behelpful to understand that the Heithaus asphaltene peptizabilityparameter, p_(a), is to some degree now viewed as related to asphaltrheological properties in terms of the Pal-Rhodes equation. The p_(a)values may be used to directly measure the volume fraction (α) of thecontinuous (maltene “solvent”) phase immobilized by the flocs ofsolvated asphaltene particles in an asphalt. Thus, reasonable Pal-Rhodessolvation parameters (K_(S)) values (which measure the size of thesolvation shell, and may be related to the stability of the asphaltsystem), may now be determined based on p_(a) data. This aspect in partfacilitated the development of the improved automated procedure nowdisclosed.

[0089] In order to comprehend the improved automated procedure it mayalso be helpful to understand the overall system. Systems according tothe present invention can, of course, take many forms. Of the manyvariations possible, the following list of scientific equipment orsupplies may be utilized in one illustrative design:

[0090] Hach DR/3000 UV-visible spectrophotometer or a 2 channelOceanOptics PC2000-UV-Vis General Purpose Spectrometer (Hach Co. andOcean Optics, Inc.), which may include the following items:

[0091] one or more 1 MHz PCI-bus A/D card w/grating or 1 MHz ISA-bus A/Dcards w/#3 Grating (350-1000 nm) (master and slave channels)

[0092] one or more cuvette holders—VIS, 1 cm Path

[0093] one or more 100μ patch optical fibers

[0094] one or more (in-line fiber optic) attenuators such as FVA-UVFiber Optic Variable Attenuators

[0095] a 3100K, 12V tungsten Halogen light source

[0096] a 200μ bifurcater optical fiber

[0097] one or more 25μ slit gratings (#3-installed on A/D cards)

[0098] a SMA splice bushing assembly

[0099] Spectra-Physics SP4270 integrator (Spectra-Physics Inc.)

[0100] ChronTrol®, Model XT-4 power switch timer (ChronTrol Corp.)

[0101] two CGS® 200 mL reaction vessels (waterjacketed)(CGS/Thermodynamics)

[0102] two FMI® metering pumps, Models: QG-50 w/R405 pump head(circulation pump; P1) & QG-20 w/RH00 pump head and RH/Q fit kits(titrant dispersion pump; P2) (Fluid Metering, Inc.)

[0103] one or more RHSYOOSTYLF PIP Pump w/fit kits (Fluid Metering,Inc.)

[0104] NesLab RTE-110 or 111M Temperature controlled circulating waterbath (NesLab Instruments, Inc.)

[0105] a Remote Sensor

[0106] Starna® 0.1 mm or 0.5 mm flow cells (such as from Starna Cells,Inc.) w/Teflon® tubing and fittings

[0107] 30 mL vials adaptable to Teflon® flow cell cover (VWR ScientificProducts Corp.)

[0108] 0.056 cm ID (0.022″) and 0.159 cm ID ({fraction (1/16)}″) Viton®tubing (VWR Scientific Products Corp.)

[0109] one or more Kontes 200 mL water jacketed reaction beakers

[0110] one or more Teflon® reaction caps/reactor covers (adaptable to25-40 mL reaction vials)

[0111] one or more VWR Model 200 Magnetic Stirrers

[0112] one or more 0.5 mm Quartz flow cells w/Teflon® tubing andfittings

[0113] one or more lab jacks

[0114] one or more 25-40 mL test tube reaction vials (cap threaded,w/Teflon® seals)

[0115] {fraction (7/16)}″ OD×{fraction (5/16)}″ ID Vinyl tubing (forwater flow)

[0116] one or more Teflon® elbows

[0117] one or more ¼″×28 to Luer Lock fittings

[0118] one or more flange fittings

[0119] one or more Flange Ferrule fitting kits

[0120] Teflon® tubing ({fraction (1/32)}″ ID)

[0121] one or more Magnetic stirring plates

[0122] Reagents such as the following may also be used:

[0123] Toluene of reagent, LC or HPLC grade (VWR Scientific ProductsCorp.)

[0124] Iso-octane (2,2,4-trimethylmethane) LC or HPLC grade (EMSciences) HPLC grade 2-Butanone (methyl ethyl ketone)

[0125] HPLC grade 2-ethyl-1-hexanol (iso-octanol).

[0126] Further, the following analysis and computer equipment may beused:

[0127] IBM-compatible PC (500 MHz minimum processing speed recommended)

[0128] 384(+)ST-RAM Memory

[0129] 10 Ge(+)Hard Drive

[0130] MS Windows 98 w/Excel 5.0

[0131] 100 MHz ZipDrive

[0132] 8-MHz HP Laser Printer

[0133] NesCom Software package

[0134] RS232 “null” 9-pin cable w/male-female adaptors.

[0135] Generally, a representative method may be accomplished asfollows. Solutions of heavy residua or asphalt may be dissolved intoluene or other higher solubility solvents (e.g., the group consistingof toluene (δ=8.9H; where H is Hildebrand units) and benzene), may beprepared in small volume reaction vials (e.g., 25 mL) and may titratedwith solvents of lower solubility (e.g., the group consisting ofaliphatic hydrocarbon substances (such as iso-octane, δ=6.9H) andalcohol substances). The added solvent amount (and the soluble substanceamount) may be noted. The term solution is used herein in a generalsense and may even include what are more specifically referred to ascolloids. Any petroleum residua that is mixed with a solvent is referredto as a solution, as is the mixture resulting from the addition oftitrant to a petroleum residua/solvent mixture. The term dissolve issimilarly defined broadly, to include even mixing that results in acolloid. Titrations may be performed by following a titration method andby using a titration apparatus, generally by first creating a solutionby dissolving a soluble substance such as petroleum residua such asasphalt into or by using a solvent (more generally mixing a petroleumresidua with a solvent), and then delivering a titrant (e.g., bycontrollably adding at titrant, and /or continually adding a titrant) ata constant flow rate via a metering pump to this test solution via apipe from what is termed generally as a titrant containment element. Anytype of titrant delivery element may be used to deliver titrant to acontainer of solution, more generally referred to as a solutioncontainment element.

[0136] Test solutions, which may be prepared at several initialconcentrations W_(a)/V_(S) (W_(a):weight of asphalt and V_(S): initialvolume of solvent) in 25 mL “test tube” reaction vials, may betemperature controlled by housing the reaction vials in water jacketedbeakers temperature regulated with a circulating water bath. Moregenerally, test solution(s) may be temperature controlled by atemperature maintenance element, which may maintain the solution at adesired temperature. The temperature maintenance element may comprise asolution containment element heat transfer element (which may comprise ajacketed beaker that surrounds the solution beaker and contains acirculating heat transfer fluid) and a titrant containment element heattransfer element (which similarly may comprise a jacketed beaker thatsurrounds the titrant beaker and contains a circulating heat transferfluid). The two heat transfer elements may be joined via tubing, orfluidicly connected, so as to form a joined heat transfer system. Twoelements are fluidicly connected if fluid from one may flow to theother. The temperature maintenance element may include a fluid pump.

[0137] The end point of the titration, referred to as the flocculationonset point, can be measured from percent light transmission versus timeexperiments using a spectrometer, in the capacity of a flocculationonset detection element such as a turbidity detector. More generally, asolution threshold change detector, or more generally, a solution changedetection element, may be used to detect any change in the solution suchas solubility reduction response such as flocculation. Detection may beaccomplished automatically by a solution change index monitor such as asolution turbidity monitor (also more specifically referred to as aflocculation onset monitor) such as a spectrophotometer, which may alsobe referred to more generally as, among other terms, an automaticsolution character determination element. This detection may be achievedby monitoring a solution change index such as turbidity.Spectrophotometrically analyzing the solution may be accomplished bycirculating the test solution with a second metering pump, through ashort pathlength flow cell, or more generally a flow cell element. Asolution circulation system may deliver solution from the solutioncontainment element to the flow cell and back to the solutioncontainment element, perhaps using a solution pump. A solution changedetection element may be responsive to said flow cell element. A firstdiscrete element, such as, for example, a structural member, isresponsive to a second discrete element if the first discrete elementreacts or responds in some way to the second discrete element. As withthe spectrophotometer, it may be configured to detect a change in lighttransmittance. Time data corresponding to V_(T), the minimum volume oftitrant required to initiate flocculation onset may be determined basedon t at maximum % T. Heithaus compatibility parameters p_(a), p_(o), andP, which can relate to colloidal stability, may be calculated frominitial condition and flocculation onset data (W_(a), V_(S), and V_(T)).

[0138] Upon achieving a threshold solution change such as flocculation,a parameter such as an added titrant amount and/or a time since theinitiation of titrant addition until threshold change may be determinedor assessed. Upon such assessment, determining a characteristic (e.g.,determining at least one Heithaus parameter, or a compatibilitymeasurement) of at least one substance of said solution may then be thenext step in the titration method.

[0139] It is important to note that the entire titration method andsystem may be electronically automated. Such automation may includeautomatically activating electronic components. It may also includeelectronic (including computerized) monitoring of parameter values suchas turbidity and maximum % light transmittance, in addition to automaticactivation of certain functions or components upon determination of acertain event (e.g., automatic delivery of additional solvent upon thedetermination of maximum % light transmittance in the reversibletitration procedure). It may comprise automatic determination of aHeithaus parameter(s), as well as automatic determination of, forexample, added solvent amounts and/or added titrant amounts, as well asof time of metered addition of titrant.

[0140] In more detail, and using the above materials, a prototype systemmay be assembled as follows. A schematic of one embodiment of aprototype overall system is shown in FIG. 1. The various components ofthis and other illustrative systems are shown in more detail in otherfigures. For example, FIG. 2 shows another embodiment of the titrationportion of the prototype design. Schematics of embodiments of 30 mLvials with a Teflon® flow cell cover is shown in detail in FIGS. 3 and4. The stir plates, lab jacks, water jacketed reaction beakers, andcuvette holders may be configured as shown in other figures. A flow cellembodiment is shown in FIG. 10.

[0141] As may be appreciated, the water jacketed reaction beakers andcuvette holders may be plumbed to a refrigerated bath/circulator using{fraction (7/16)}″ OD×{fraction (5/16)}″ ID Vinyl tubing, assortedTeflon® or vinyl 45° elbows ({fraction (5/16)}″ OD) and couplers({fraction (5/16)}″ OD). The tubing, couplers, and elbows may befastened using plastic hose clamps or the like, of course. Further, asshown, the vinyl tubing and water jacketed reaction beakers may beinsulated with styrofoam refrigeration tubing and black duct tape or thelike. The refrigerated bath/circulator RS232 port may be connected tothe computer cable serial port using a 6′-RS232 “null” 9-pin cable.

[0142] Cuvette holders and metering pumps may also be configured to thelab jacks as shown. A sample circulator and one or more circulatormetering pumps may be plumbed to the flow cells and sample reactionvials using Teflon® tubing and fittings, which are internally coatedwith a Teflon® surface coating, as may be any other pipings, conduits,caps, or containers. More generally, such system components may have areduced flow reisistance internal surface. Other coatings other thanTeflon® that similarly reduce frictional force exerted against a passingfluid may be used also, or no special coating over the internal surfaceof the tubing may be used at all. A titrant dispenser may also be used.In some embodiments, a stand or platform may be utilized directly behindor adjacent stir plates and lab jacks. As shown, it may be desirable toplace each titrant pump on a stand, directed toward the reaction beakerto which it will titrate. Further, the titrant pumps may be plumbed tothe titrant reservoir and sample reaction vials w/Teflon® reaction caps(or lids)/reactor covers using a 2-RH/Q Fit Kit (Teflon® tubing (e.g.,{fraction (1/32)}″ ID) and Flange fittings. A Luer-Lock coupler may befastened to the tubing end leading to the reaction vial from the titrantpump. A short-needle syringe (e.g., blunt ended-19 gauge, 1″ longneedle) may be inserted into Luer-Lock couplers. 50 mL beakers or thelike may be placed adjacent to the pumps to hold-in-place the syringeneedle-tubing ends.

[0143] As mentioned, FIGS. 1 and 2 show schematics of prototypeapparatus used to perform automated titration tests. Power suppliesrunning from the spectrophotometer, integrator, and water bath, circuitsA, B, and C respectively, may be connected to a ChronTrol® power switchtimer, or more generally a system activation element. This can permitprogrammable activation of the instruments. Additionally, or instead, acomputer such as a personal computer for example, may be configured toelectronically interact with one or more of the following—aspectrophotometer, an integrator, any pumps that may exist, and aChronTrol® power switch. A computer may be used in place of either theChronTrol® power switch and/or the integrator. Any device that mayindicate the onset of a solution change, including but not limited to anintegrator, a personal computer, or a combination of the two, maygenerally be referred to as a threshold change indicator, or morespecifically, a light transmittance threshold change indicator.

[0144] Two CGS® 200 mL reaction vessels (water jacketed) arranged inseries may be attached to the water inlet and outlet of the NesLabRTE-110 circulating water bath. An FMI® metering pump, Model QG-50w/R405 pump head (P1) may be connected to the Starna® 0.1 mm pathlengthflow cell (housed inside of the spectrophotometer) via a 15 cm long,0.159 cm ({fraction (1/16)}″) ID piece of Viton® tubing. A second andthird piece of 0.159 cm ({fraction (1/16)}″) ID Viton® tubing, 10 cm and20 cm long, respectively, may extend from the metering pump and from theflow cell to a 30 mL reaction vial screwed into a Teflon® cover. Thereaction vial w/Teflon® cover may be positioned inside of one of theCGS® 200 mL water jacketed reaction vessels (WJ2). A second FMI®metering pump (P2), Model QG-20 w/RH00 pump head (titrant dispersionpump) may be connected to the other CGS® 200 mL water jacketed reactionvessel, which may act as a titrant reservoir (TR), via a 25 cm longpiece of 0.056 cm (0.022″) ID Viton® tubing. A second, 20 cm long pieceof 0.056 cm (0.022″) ID Viton® tubing may extend from the titrant pump(P2), through a predrilled hole in the Teflon® cover to the reactionvial positioned inside of a CGS® 200 mL water jacketed reaction vessel(WJ2).

[0145] The spectrophotometer, temperature bath, and integrator may beactivated (circuits A, B and C) at least about 1 hour before testing ofsamples begin. As one way to achieve activation and automation, allthree devices may be connected to a ChronTrol® power switch timer andmay be activated by typing “CIRCUIT”, “1”, and “ON”, “CIRCUIT”, “2”, and“ON”, and “CIRCUIT”, “3”, and “ON” on the ChronTrol power switch timerkey pad. The temperature bath may be set to a temperature of 25° C. (77°F.). Fine tuning of the temperature control or feedback may be requiredonce the temperature of the water bath has stabilized (e.g., inapproximately 1 hour).

[0146] Liquid Chromotography-, LC-grade iso-octane (titrating solvent)may be added to the titrant reservoir (TR). The level of titratingsolvent may be added to within 1 cm of the top of the reservoir. Titrantmay be added to the reservoir prior to activation of the water bath,allowing the titrant to also come to temperature equilibrium.

[0147] The spectrophotometer and integrator parameters may be set oncethe spectrophotometer has warmed up. The UV-visible spectrophotometercan be set in percent transmittance detection mode by depressing “4”,“signal”, and the “% T” keys on the spectrophotometer soft key pad. Thewavelength selection knob may be set to λ_(D) (nm)=740 nm. The zeroscale and full scale settings of the spectrophotometer may be initiallyset at 0 percent transition and 100 percent transition, respectively, bydepressing the following keys on the soft key pad of thespectrophotometer: “zero”, “0”, and “full”, “1”, “0”, “0”. Further, itshould be noted that it may be desirable or necessary to reset the fullscale and zero scale settings for each sample, depending on the sampleresponse once testing has begun.

[0148] The spectrophotometer signal average is set to 10 by keying in:“signal”, “1”, “0”. The integrator, when activated, may then prompt theuser for the date and time. Once the date and time are entered thefollowing settings may be entered on the soft key pad: “shift”, “shift”,“P”, “W”, “=”, “shift”, “2”, “0”, “0”, “enter”. This may represent oneway of setting the peak width to 200. Further the commands: “shift”,“shift”, “P”, “T”, “=”, “shift”, “1”, “0”, “0”, “enter”, may be enteredto set the peak threshold to 100. Attenuation may be set to 1024 by thecommands: “atten”, “1”, “0”, “2”, “4”, “enter”. The chart speed may thenbe set to 1.0 cm/min using the commands: “chtsp”, “1”, “enter”.

[0149] The following procedure may be used to re-zero thespectrophotometer relative to a toluene reference blank prior to sampletesting. Two 30 mL vials may be joined or taped together and toluene maybe added to one of the vials. The two joined-together vials may beplaced in a ring stand clamp next to the solution circulating pump (P1).Toluene may then be drawn from the first vial and deposited into thesecond (empty) vial, via Viton® tubing attached to the circulating pump(P1). When approximately one half of the toluene has been pumped intothe second (empty) vial, the “re-zero” key on the spectrophotometer keypad may be depressed. The reading on the spectrometer may then read100.0 percent transmittance. This may fluctuate perhaps ±0.5 percenttransmittance. During the re-zeroing of the spectrophotometer, thesolution circulating pump (P1) may be adjusted to a flow rate of 8mL/min. The end of the Viton® tubing in the vial containing toluene maybe removed and the circulating pump system may be pumped clear ofsolvent.

[0150] The samples may then be prepared as follows. Samples of asphaltmay be weighed into 30 mL vials adaptable to a custom design Teflon®cover as shown in FIGS. 3 and 4. Care may also be taken during weighingnot to deposit asphalt on the sides of the vials. Two sets of thefollowing representative sample weights may be prepared; 0.200 g, 0.400g, 0.600 g, and 0.800 g (all ±0.002 g). The actual measured weight ofeach sample, measured to an accuracy of ±0.0002 g, may then be recordedas W_(a). Samples may then be labeled with information such as: Operatorinitials; notebook number; page number; sample set letter; samplenumber. Of course, several sets of samples may be weighed into vials atone time. Here, it may be noted that if dry samples are to be stored forany length of time, e.g., more than a day or perhaps more than even just4 hours, it may be desirable for them to be capped under a blanket ofargon gas.

[0151] The samples to be tested within 1 day of weighing may then bedissolved in 1.000±0.002 mL of LC-grade toluene. This may be added toeach vial using a 2.500±0.002 cc syringe. The volume of solvent added toeach sample may then be recorded as V_(S). Approximately 1 to 2 hoursmay be required to completely dissolve all samples at room temperature.For best results it may be desirable for samples dissolved in solvent tobe tested on the same day they are prepared.

[0152] As an improved design, a solution circulation system (SCS) may beassembled as shown in FIGS. 1, 2, and 9 as follows. The SCS may beassembled using a RHSYOOSTYLF PIP” FMI fluid metering pump, {fraction(1/32)}″ ID-Teflon® tubing and Flange Ferrule fitting, and a 0.1-0.5 mmflow cell. The leg stands originally provided with the pump may bemodified by installing 2-½″ leg extensions to each of the four legs ofthe pump. This may allow the pump to sit high enough, directly over theflow cell cuvette holder, and adjacent to the Kontes 200 mL waterjacketed reaction beaker to operate properly. The pump may be specifiedto have a ⅛″ piston diameter with a maximum piston travel distance of¼″. This may help to reduce the volume of test solution in the SCS atany given time period during the analysis. Three pieces of {fraction(1/32)}″ ID-Teflon® tubing may be fastened between the pump and flowcell, flow cell and reaction vial, and from the pump to the reactionvial using Flange Ferrule fittings. The lengths of Teflon® Tubing usedmay be 7-8 mm, 4-5 mm, and 15-16 mm, respectively. The total volume ofthe SCS might be designed so as not to exceed ˜10% of the volume of thestarting test solution. The circulation rate of the SCS may also bemaintained at a minimum flow rate of 8.0 mL/min, where faster flow ratesare permitted. The “RHSYOOSTYLF PIP” FMI fluid metering pump may befurther specified to have an organic solvent resistant piston sleeve.

[0153] As mentioned, it may be desirable to design the total volume ofthe SCS so as not to exceed ˜10% of the volume of the starting testsolution, or in other words, 10% of an initial solution volume, whereinitial refers to the time before any addition of titrant. The SCS maythus be a low volume solution circulation system. This may serve toreduce or eliminate “Flocculation Peak Shift”. Flocculation Peak Shiftmay be characterized by flocculation peaks being shifted to lower valuesof flocculation onset. This may be due to too large of a volume of testsolution (e.g., >about % 10) residing within the SCS, relative to thevolume of solution in the vial during a test run. With the currentconfiguration, test solutions are prepared using 0.8 g, 1.0 g, 1.2 g,etc. of test sample (asphalt) per 2.0 mL of solvent (toluene). This mayserve to eliminate any significant flocculation peak shift.

[0154] Reaction containers may be configured as shown in FIGS. 3, 4 and8 as follows. Teflon® reaction caps/reactor covers (adaptable to 25 mLreaction vials), and 25 mL test tube reaction vials may be used as thereaction containers or as reaction vials. The Teflon® reactioncap/reactor cover may be adaptable to 25 mL test tube reaction vialswhich are designed to fit inside a Kontes 200 mL water jacketed reactionbeaker. The Teflon® reaction cap/reactor cover may hold a 25 mL testtube reaction vial, suspended within the beaker, further reducing thelength of {fraction (1/32)}″ ID-Teflon® tubing needed in the SCS. Theunique round bottom design (e.g., “test tube” shape) of the 25 mL testtube reaction vials may be used to promote uniform, and undisturbedstirring of the test solution during operation. A Teflon® reaction capor lid, referred to more generally as a Teflon® lined solutioncontainment element cap, may achieve a hermetic seal, effectivelyisolating the internal gaseous environment of the solution from theenvironment external of the solution containment element and thesolution circulation system, for example. This hermetic seal is a typeof gas exclusion element; excluding gas could also result from anapparatus or technique other than hermetic sealing. The term excludinggas from the solution does not necessarily mean all gases, as inertgases such as Argon, e.g. (or other gases other than oxygen) may existin contact with the solution. The titration apparatus may comprise asolution containment hermetic seal such as a solution-titrant compatibletight fitting titration test container cap (or lid) which would excludeundesired gases such as oxygen from the solution containment element,and/or a titrant containment element hermetic seal, and/or ahermetically sealed titrant delivery element which would serve toisolate titrant and solution from the gaseous environment surroundingand external to their containment elements. The titration method, ormore specifically the step of excluding gas from the solution, maycomprise the step of pressurizedly purging substantially all oxygen fromthe solution containment element, as well as from other systemcomponents that might otherwise allow oxygen to contact the solution.This pressured purging may comprise the step of using an inert gas suchas argon.

[0155] The entire procedure may proceed through a series of steps whichlend themselves to both repeatability and practicality. As one aspect,sample preparation may include steps such as the following procedure.

[0156] 1. Test samples may be prepared in 25 mL “test tube” vials(w/Teflon® lined seal 20/400-threaded caps).

[0157] 2. Samples may be prepared in triplicate by transferringapproximately 0.8 and 1.0 g of heavy residua or asphalt to two taredreaction vials and measuring sample masses to an accuracy of ±0.0005 g.All samples may be purged with Argon (Ar) gas and the vials may besealed with Teflon® lined caps.

[0158] 3. Prior to testing, the prepared samples may be dissolved in2.000±0.001 mL of toluene (HPLC-grade). The reaction vials may bere-sealed with Teflon® lined caps and stored away from sunlight. One andone-half to two hours may be allowed for sample dissolution. A minimumof six hours is preferred for complete dissolution, and even a 24 hourperiod is strongly recommended.

[0159] Instrument Initialization may include steps such as the followingprocedure.

[0160] 4. The spectrometer halogen lamp may be activated and allowed towarm up. Note that the tungsten Halogen lamp may require approximately 1hour of warmup time.

[0161] 5. The refrigerated bath/circulator may be activated. If a NesLabRTE-111-M refrigerated bath/circulator is used, a power switch islocated on the left side panel of the “Micro” processor. As to thisstep, it may be noted that if the bath/circulator fails to power up, thecirculator's microprocessor may need to be reset. The NesLab “Micro”processor may display “Prog” if not reset. This may occur if theCirculator alarms have been activated during previous usage. To resetthe bath/circulator, simultaneously one may depress the “0” soft key onthe bath/circulator “Micro” processor key pad while activating the mainpower switch. The NesLab “Micro” processor will read “OFF”. Toreactivate the bath/circulator, press the “On/Off” soft key on the“Micro” processor key pad. The “Micro” processor may now display atemperature reading in degree centigrade (° C.).

[0162] 6. The remote sensor computer software up-link may then be setfrom the NesLab “Micro” processor keypad by depressing: “Sensor” then“Enter”, then “RS232”, and then “Enter”. The NesLab bath/circulatorshould now be controlled from the computer.

[0163] 7. The NesCom v 2.01 windows software may be activated by doubleclicking the NesCom icon and the following commands: Files, New,Controller and “Micro” processor bath and answering “yes” when prompted;“Is the Remote Sensor Enabled?” Note the micro processor bath icon maybe displayed in“BLUE” when in standby mode.

[0164] 8. Double clicking the “blue” micro processor bath icon, maypermit one to confirm that the corn address is set to “1”, by selectingOK.

[0165] 9. To initialize a working temperature program, one may open thefollowing files from the main window; Program, Program Parameters . . ., and Open. Double clicking the file “ambientTemphold.prg”, andselecting OK is the current command structure.

[0166] 10. The “Micro” processor bath program may then be brought onlineby opening the following files from the main window: View, and ProductPanel, and by answering “yes ” when prompted; “Confirm that Unit is on”.The temperature and setpoint values may now be displayed. Further, itmay be noted that the “Micro” processor bath icon may display in GREENwhen activated.

[0167] 11. The operator may next minimize the NesCom and “Micro”processor Bath windows. The metering pumps calibration and the like maythen proceed including steps such as the following procedure.

[0168] 12. To calibrate the titrant pumps, the operator may mount a1.000 mL syringe-graduated cylinder to a small lab stand using a testtube clamp or the like. Positioning the stand next to the titrant pumpmay assist.

[0169] 13. The operator may then time the flow rate of each titrant pumpwith a stop watch, and each may be adjusted to a set value such as 0.300mL/min or even 0.500 mL/min, the latter of which may also be a maximum.

[0170] 14. To calibrate the circulation pumps, a 10.0 mL graduatedcylinder may be mounted to a small lab stand using a test tube clamp.This may be positioned next to a titrant pump.

[0171] 15. With a stop watch, the operator may time the flow rate ofeach circulation pump and adjust each flow rate to a value such as 8.0mL/min, which may also be a minimum. The spectrometer portion of thesystem may then be set up through steps such as the following procedure.

[0172] 16. If the currently preferred brand is used, the OceanOpticsspectrometer(s) may be activated by loading the OOIBase32 software fromWindows, and double clicking the OOIBase32 icon to load the program. The“Configure Hardware” window may then be displayed. The operator maychange the “A/D Converter Type” to “ADC 1000/PC2000”, and then selectOK. The window; [Spectrum 1] may then be displayed.

[0173] 17. The [Spectrum 1] window may be configured as the masterspectrometer by default. Note, to activate additionalspectrometers/windows, e.g., Slave 1 and Slave 2 spectrometers, selectNew from the File menu. Change the “Configure Hardware”, i.e. change the“A/D Converter Type” to “ADC 1000/PC2000”, and select OK. A second[Spectrum 2] window may be displayed for the Slave 1 spectrometer. Todisplay the [Spectrum] windows simultaneously, select the Window menuthen the Tile Vertically menu. Open the following files fromtheOOIBase32 main window; Spectrometer, and Open Configuration . . . ,select the file “PC0A000.spec”, then Open. The spectrometer address filemay differ for each spectrometer bus A/D card present in the computer.See the manufacturer's specification for configuring any specificspectrometer address for a particular “AA0A000.spec” file. Either aPCS0A000.spec and/or IS0A000.spec file may correspond to the Slave 1 andSlave 2 spectrometers available with a particular instrumentarrangement.

[0174] 18. The operator may then set and calibrate each spectrometer fortransmission mode operation as follows; in Scope Mode, the operator mayadjust “Integ. Time (sec)” and the aperture such that at 740 nm theintensity is approximately 3500 units, i.e. with the aperture open, set“Integ. Time (sec)” to 14 to start. One may even set both the “Average”and “Boxcar” settings to 100 initially, then close the Halogen lampshutter and select “Ctrl+D” (Dark spectrum). Open the Halogen lampshutter and select “Ctrl+R” (reference spectrum). Select “Ctrl+Shift+T”or select the [T] icon to change the spectrometer detection mode toTransmission Mode. Repeat this procedure for all remaining open spectrumwindows that will be operated. The data acquisition portion of thesystem may then be set up through steps such as the following procedureas illustrated using the OceanOptics Spectrometer.

[0175] 19. A Time Acquisition Channel may be activated for a spectrumwindow, e.g., the OOIBase32 window; [Spectrum 1], previously opened.From the OOIBase32 main window, the operator may single click the headerof the desired [Spectrum 1, 2, . . . ] window, and select TimeAcquisition, then Configure, then Configure Time Channels. The TimeAcquisition Channel Configuration window for Channel A, [Spectrum 1]window may now be displayed.

[0176] 20. The operator may then enable the channel, by single clickingthe blank boxes next to Enabled and Plotted, a check mark may bedisplayed in each box.

[0177] 21. The “Spectrometer Channel” may then be set to Master if the[Spectrum 1] window has been selected as the (PC0A000.spec) spectrometerconfiguration. Note here that the “Spectrometer Channel” selection maychange depending on the spectrometer configuration displayed, e.g., toenable the Slave 1 channel, select the [Spectrum 2] window by singleclicking the header of the window and select Time Acquisition, thenConfigure, then Configure Time Channels, set the “Spectrometer Channel”to Slave 1 for the PCS0A000.spec file associated with the window.

[0178] 22. The operator may then set the detection wavelength byclicking inside the box next to “Wavelength (nm)” and typing in 740 toset the detection wavelength to 740 nm. Here note that the threeremaining parameters may be pre-set values and may remain as; Factor(multiply)=1, Bandwidth (pixels)=0, and Offset (add)=0. Select OK toconfirm the settings and exit.

[0179] 23. The operator may then set the software to stream data tofiles for Master and Slave channels, from the Time Acquisition menu, byselecting Configure, then Configure Acquisition . . . , and checking theStream Data to Disk and Show Values in Status Bar boxes. Note that itmay be necessary to disable Save Full Spectrum with Each Acquisition,Save Every Acquisition, or Continue Until Manually Stopped if they areselected.

[0180] 24. The time file settings may be set by selecting the TimeAcquisition menu, and selecting: “Write Data to Disk Every”=1acquisition, “Initial Delay”=0, “Frequency”=100 milliseconds, and“Duration”=8 Hour.

[0181] 25. To save the “percent Transmission” versus “time” data to theWindows Desktop, the operator may need to select the “Stream andAutosave Filename” box and change it to: C:\Desktop\timetestMASTER.Time.Select OK to accept the file name settings and exit. This file name mayrepresent the file of the first of two solutions that will be titratedfor a given asphalt in a sample set. Normally theC:\Desktop\timetestMASTER.Time file may correspond to the more dilutesolution in the sample set. A second streamed data file may be saved as“C:\Desktop\timetestSLAVE.Time”, such as corresponding to the moreconcentrated solution data file in the sample set.

[0182] 26. The operator may then activate the time channel window “readyfor testing” by opening Time Acquisition and selecting the Activate TimeAcquisition option from the active window, [Spectrum 1, 2, . . . ].Here, note that the time acquisition icon tool button may be used toactivate the Time Acquisition menu as an alternative. The titration andcirculation pumps may then be calibrated through steps such as thefollowing procedure.

[0183] 27. Prior to sample testing, the circulation pumps (CP) andtitrant delivery pumps (TDP) may be adjusted to predetermined flowrates.

[0184] 28. The operator may set each CP-flow rate by placing the intaketube in a vial of toluene and the output tube in a 10.0 mL graduatedcylinder. The flow rate may then be timed with a stop watch and theCP-flow rate may be adjusted to 8.0 mL/min, which may also be a minimum,each perhaps reported to an accuracy of ±0.1 mL/min.

[0185] 29. The TDP-flow rates may similarly be timed and adjusted to0.300 (or 0.500 which may also be a maximum) and report to an accuracy±0.001 mL/min. The spectrometer may then be re-zeroed through steps suchas the following procedure.

[0186] 30. The operator may fill a 50 mL beaker half-full withHPLC-grade toluene and may pump the toluene through the circulationpump/flowcell system into a second 50 mL beaker. Likely it may bedesirable to discard the first few milliliters of solvent and replacethe beaker, and continue the process until the disposed solvent isclear.

[0187] 31. The operator should then verify that the spectrometer is in %T-mode, obtain a Dark and a Reference spectrum for the activespectrometer. The operator closes the Halogen lamp shutter and select“Ctrl+D”. Then, the operator may open the Halogen lamp shutter andselect “Ctrl+R”. This step may be repeated prior to each sample tested.

[0188] 32. The operator may then adjust the spectrum % T scale byselecting View, then Spectrum Scale, then Set Scale. When the Scaleadjustment window appears, set the “X-Axis (nm) Minimum” value may beset to 739.99, and set the “X-Axis (nm) Maximum” value may be set to740.1. A titration procedure may then be performed through steps such asthe following procedure.

[0189] 33. The operator may place a stir bar into a 25 mL “test tube”vial containing the 0.400 g/mL sample. The Teflon® cap/Reactor cover maythen be screwed onto the vial. The operator may then set thevial/reactor cover into the water filled 200 mL jacketed reaction beakerand engage the stir bar. The stir plate may be set to speed “4”.Operation may then proceed to allow sufficient time (3-5 minutes) forthe sample to come to temperature equilibrium.

[0190] 34. The CP-tubing ends may be inserted through the holesavailable in the top of the Teflon® cap/Reactor cover. Here the operatormay adjust the CP-tubing ends either up or down to prevent them fromhindering the stir bar.

[0191] 35. The titrant pump dispenser-tube end may then be insertedthrough an available hole in the Teflon® cap/reactor cover.

[0192] 36. The operator may then initiate the titration experiment bysimultaneously engaging the titrant pump, activated from the power strip(Switch #1), and the time acquisition play icon, activated from withinthe [Spectrum ] window with the mouse. Here, note that when the timeacquisition play icon is activated, the time acquisition pause icon andthe time acquisition stop icon may also become activated. These iconsmay be used to pause, or stop the stream of data to the time acquisitiondata file during a test.

[0193] 37. The operator may then monitor the status of the titration onthe status bar located at the bottom of the [Spectrum] window. A timeplot may also be displayed on the spectrum for monitoring. The spectrumTransmission intensity (redline) may increase over time, then decrease.As this value increases then decreases, the spectrum line will likely beobserved to rise then fall, this signifies that the flocculation onsetendpoint has been reached. The operator may then allow a few seconds oftime to pass to confirm the flocculation onset point and then act todeactivate the titrant pump (Power Strip Switch #1), and the datastreaming (time acquisition stop icon). Note that each spectrum windowtime acquisition play icon and titrant pump On/Off switch may be set tobe activated and deactivated independently of other time acquisitionplay icons and titrant pump On/Off switches.

[0194] 38. When the test is complete, the operator may remove thecirculation pump intake tube end from the sample, and pump the residualsample solution back into the reaction vial. It may then be desirable toremove the second tube end and pump several milliliters of toluenethrough the system using 50 mL beakers.

[0195] 39. The tested sample may then be removed, the vial rinsed, andaired in the hood. The Teflon® reactor cover may then be cleaned anddried with a cold-trap vacuum line.

[0196] 40. The above steps may also be repeated to titrate additionalsamples. In repeating steps, it may be helpful to note that tests may beperformed by titrating a sample at two concentrations, e.g., 0.400-g/mLand 0.500 g/mL. It may be desirable to save the 0.400-g/mL sample run asC:\Desktop\timetestMASTER.Time and the 0.500-g/mL sample run asC:\Desktop\timetestSLAVE.Time.

[0197] In the above testing, sample runs may be performed by loadingvials (30 mL) of sample into the second water jacket (WJ2), generallyfrom least to most concentrated in solution, by carefully placing asmall stir bar into a vial of the solution and screwing the vial intothe Teflon® cover. The vial/cover may be placed into the second waterjacket (WJ2). The two ends of the Viton® tubing, which run from thecirculating pump (P1) and from the flow cell, respectively, may beplaced through holes in the cover down into the solution. As the asphaltsolution circulates through the flow cell, the percent transmittancereading of the spectrophotometer may decrease, then stabilize at someminimum value of percent transmittance, corresponding to the percent oflight transmitted through a solution of asphalt in toluene with notitrant added. One end of the Viton® tubing running from the titrantpump (P2) may be placed down into the vial well above the surface of theasphalt solution. A probe thermometer (not shown)may also be placed downinto the test solution and used to monitor the temperature of thesolution as the titration proceeds. To begin the titration, the titrantpump (P2) and the integrator may be started at the same time.

[0198] Further, in establishing the titrant flow, a maximum titrant(2,2,4-trimethylpentane-iso-octane and methyl ethyl ketone-MEK) flowrate may be important. In one embodiment, a maximum titrant additionrate not to exceed 0.5 mL/min has been determined to work as the mostefficient flow rate for the current instrument configuration.Furthermore, higher viscosity titrants, such as 2-ethyl-1-hexanol(iso-octanol) may be used in place of 2,2,4-trimethylpentane(iso-octane) or methyl ethyl ketone (MEK). In such use, the maximumtitrant addition rate may be selected so as to not exceed 0.2 mL/min toproduce repeatable test results. Adding a titrant at maximum rate, ormore generally adding a titrant at an optimal solubility reductionresponse rate, may be important for efficient and accurate operation ofthe titration apparatus. While of course, such rates may be varied,these maximum titrant addition rates have been determined based on anumber of samples tested. Regardless of the rate used, it may be notedthat the reagent grades may also be important to the procedure. Forexample, all of the reagents; 2,2,4-trimethylpentane (iso-octane),toluene, 2-ethyl-1-hexanol (iso-octanol), methyl ethyl ketone (MEK), andthe like used in this procedure may be at a minimum of HPLC grade.

[0199] As mentioned above, as the titration proceeds a flocculation peakwill likely develop. A representative example of such is shown in FIGS.5, 6 and even FIG. 7. As may be understood, the initial increase inpercent transmittance (% T) of the flocculation peak, plotted as afunction time in which titrant is added at a constant flow rate, is dueto the dilution of the test solution as iso-octane is added. During thistime period, dispersed phase molecular associations likely remain insolution. A maximum % T value is then reached. At this point, theintegrator may print out a retention time. The % T value versus timeplot, such as that shown in the FIGS. 5, 6, 7 and 12 then may decreasedue to the scattering of light as dispersed phase molecular associationsbegin to precipitate from the test solution. The flocculation onsetpoint is then taken as the retention time value recorded at maximum % T.At the flocculation onset point the temperature of the solution may thenbe recorded. FIGS. 5 and 6 show a plot of percent transmittance versustime for a flow rate of υ_(T) (mL/min) for four samples of SHRP coreasphalt AAD_(—)1 dissolved in toluene at four different concentrations.While, of course, displays may be varied, one type of display that maybe provided by the analysis software is shown in FIG. 12.

[0200] In addition, the reversible Heithaus titration procedure may beused to measure Heithaus parameters p_(a), p_(o) and P on single samplesbased on a “back” titration technique. This variation may be performedby first preparing a 1.0 g sample of asphalt dissolved in 2.0 mL oftoluene in 30 mL vials, then titrating the solution with iso-octane(2,2,4-triethylpentane at a constant flow rate in accord with the aboveprocedure. As the titration proceeds, each onset of flocculation may beclosely monitored by monitoring a solution change index, or moregenerally a parameter, such as turbidity, of the solution. When thefirst flocculation onset caused by the addition of the titrant isobserved (or more generally, upon achieving a threshold solutionchange), signified by, for example, a change in direction of the percenttransmittance versus time plot, the step of adding a solvent to thesolution, such as quickly adding a 1.0 mL aliquot of toluene (forexample) may be performed. More generally, upon achieving a thresholdsolution change, the step of altering a character of the solution toeliminate (where eliminate also means substantially eliminate) the firstthreshold solution change may be performed. This addition of toluene,e.g., or other solvent to the sample solution as the titration continuesuninterrupted tends to mostly re-dissolve the sample, effectivelyachieving a lower solubility parameter for the solution and by dilutingthe sample to accommodate a second, and possibly a third measurement ofthe flocculation onset in-situ. After flocculation is observed, the stepof preliminarily assessing a parameter (such as a Heithaus parameter(s)and/or compatibility and/or added titrant amount since any priorflocculation that may have existed, and/or time since any priorflocculation (or since the initiation of titrant addition)) may beperformed. Indeed, the experiment may repetitively achieve additionalthreshold solution changes, which may each be detected by a repetitivesolution threshold change detector that may comprise, for example, anintegrator and/or a computer program, among other components. As in anytitration method, the temperature of the solution may be controlled by atemperature control element such as a circulating water bath. FIG. 11shows a plot of percent transmittance versus time (at constant titrantflow rate) for such a reversible Heithaus titration experiment of SHRPcore asphalt AAA-1.

[0201] The above procedure may be fully automated if a programmable pumpor solvent dispenser is used to deliver the “back titrant” toluene tothe sample solution as indicated by differential integration of theflocculation onset point, as the titration proceeds. More generally, anydetermination of the maximum % transmittance value may suffice. Uponsuch determination, an automatic solvent introduction system, or moregenerally a solvent introduction system-may be activated. A solutioncharacter alteration element, such as a metered solvent addition system(which may comprise a pump), may be responsive to a solution thresholdchange detector via, e.g., an integrator and/or computer that monitors aparameter such as % transmittance v. time of titrant addition (theintegrator and/or computer may signal the maximum of this graph).Addition of may be performed in a metered fashion by, e.g., a meteredtoluene addition element or a metered benzene addition element.

[0202] As one example, Table 1 lists some experimental values, averagesand standard deviations in measured values of p_(a), p_(o) and P foreight SHRP core and six non-core asphalts using the reversible Heithaustitration technique.

[0203] Finally, at the completion of a run, the Viton® tubing runningfrom the circulating system may be drawn up out of solution and theremaining solution in the circulating system may be pumped out into thesample vial. The tubing may then be placed into a vial containingtoluene. Clear toluene may be circulated through the pump (P1), tubing,and the flow cell clearing the system. The Viton® tubing running fromthe titrant pump (P2) may then be placed into the top of a graduatedcylinder and the flow rate of the titrant may be timed with a stopwatch. A second sample may then be loaded into the system and theprocedure repeated. When testing is completed, all glassware used duringthe procedure may be rinsed with wash toluene and allowed to dry in avented hood. The circulation pump may be flushed with fresh LC-gradetoluene, and then pumped dry of solvent, and all components of thesystem may be shut down.

[0204] As mentioned, the Heithaus parameters can be determined from theabove procedures data calculation may involve the following variables:

[0205] Sample weights, W_(a) (g)

[0206] Volume of solvent (toluene), V_(S) (mL)

[0207] Detection wavelength, λ_(D) (nm)

[0208] Titrant flow rate, υ_(T) (mL/min)

[0209] Retention time at peak apex (flocculation onset), t_(R) (min)

[0210] Solution temperature at flocculation onset, T_(soln) ({grave over(η)}C)

[0211] The volume of titrant (V_(T), mL) added to each sample toinitiate flocculation may be calculated as the product of the time(reported as the peak retention time t_(R), min) required to delivertitrant at a flow rate of {umlaut over ()}_(T) (mL/min) to the testsolution. V_(T) (mL) may be calculated as follows:

V_(T)=t_(R)υ_(T)   (1_(—)1)

[0212] Values of V_(T), V_(S), and W_(a) may be used to calculateflocculation ratios and dilution ratio concentrations, FR and C, foreach run (which may consist of a set of test solutions of differentconcentrations of a given asphalt) using the following relationships:

FR=V _(S)/(V _(S) +V _(T)).   (1_(—)2)

[0213] and

C=W _(a)/(V _(S) +V _(T))   (1_(—)3)

[0214] A linear analysis may be used to derive the equation for the lineFR=aC+b using values of FR_(i) plotted versus values of C_(i). Heithausparameters may then be calculated by extrapolating the line to the x andy axis, where the x and y intercepts are formally referred to as thedilution ratio minimum (C_(min)) and the flocculation ratio maximum(FR_(max)), respectively:

b=FR_(max)@C−0   (1_(—)4)

[0215] and

−a/b=C_(min) ⁻¹@FR=0   (1_(—)5)

[0216] Using values of FR_(max) and C_(min), Heithaus parameters p_(a),p_(o), and P may be calculated as follows:

P _(a)=1−FR _(max)   (1_(—)6)

p _(o) =FR _(max)[(1/C _(min))+1]  (1_(—)7)

P=p _(o)/(1−p _(a))   (1_(—)8)

[0217] As part of a representative automated routine, the Heithausparameters may be calculated using a Excel macro, named AFTCalc.xls. Toopen this, an operator need only “double click” the AFTCalc.xls filefrom the list of desktop files, and “Click” the Enable Macro option whenprompted. Next the operator could select the Tools pull down menu, thenselect Macro, then □Macro . . . , (Alt+F8), and finally Run. The macromay open a template file, such as a AFT Template with graphs.xls and thepreviously saved time files; C:\Desktop\timetestMaster.Time andC:\Desktop\timetestSLAVE.Time. When the macro has completed thecalculation of Heithaus parameters, the operator may need only save thefile with an appropriate name.

[0218] It is important to understand a few of the more practicalimprovements in production technique and asphalt processing that areenabled by this accurate Heithaus parameter determination method. It isnow possible to accurately predict the compatibility of an asphalticcomposite, more commonly known as an asphalt blend, and thus to moreefficiently and cost-effectively prepare a compatible asphalt compositein commercial quantities. An asphalt producer such as a refiner mayobtain a quantity of a first type of asphalt and a quantity of a secondtype of asphalt, which may be of lesser quality or lesser cost per tonthan the first quantity of asphalt. Perhaps also there may exist a thirdtype. The asphalts may merely be of different stocks. Essentially, theproducer may use the automated Heithaus parameter determination methodto affirmatively and accurately an optimal asphalt mix ratio to achievea desired result such as cost savings. A producer may wish to mix two ormore different types of asphalt (for example, asphalt from differentstocks) in optimal mix ratio such that the resulting composite is stillcompatible. It may be that the producer has a first superior characterasphalt substance and a second inferior asphalt substance. In order todo this, the producer (or more generally a tester) may create a firstasphalt composite by mixing in a predetermined ratio two or more typesof asphalt to create a first intermediate asphaltic composite. Thetester may then use the automated Heithaus parameter titration apparatusand method described herein to accurately determine a first set ofHeithaus parameters, which may then be used to accurately generate afirst compatibility measurement of the first intermediate compositeblend (also known as accurately determine the long term compatibility).The tester may then also create an additional intermediate asphalticcomposite with predetermined ratio(s) that is(are) different from thefirst asphaltic composite. The tester may then use the automatedHeithaus parameter titration apparatus and method described herein toaccurately determine an additional set of Heithaus parameterscorresponding to each of the additional intermediate asphalt compositesas may have been created. The next steps would involve comparing aplurality of compatibility measurements of the intermediate asphalticcomposites and then selecting an optimal asphalt mix ratio based uponthis plurality of compatibility measurements. Upon such selection, theasphalt producer would then mix a tonnage amount of the different typesof the asphalts in order to arrive at an optimal compatible composite.Relatedly, a titration apparatus used in order to determine thesuitability (by measuring, e.g., compatability) of a composite asphaltmay be said to comprise a composite asphalt containment element; atitration apparatus used in this capacity is said to be an optimal mixratio determination system. To improve efficiency, such an apparatus maycomprise multiple composite asphalt containment elements, as well asmultiple solution character determination elements, such asspectrophotometers and/or computers that may be used to automaticallydetermine Heithaus parameters. Any component that serves to aid in thedetermination of Heithaus parameters, such as, but not limited to, aspectrophotometer and/or a computer and/or an integrator may be usedmultiply as a multiple Heithaus parameter determination element.

[0219] Another related production technique enabled by the presentinvention's accurate Heithaus parameter determination has to do withreplacing a certain type of asphalt that perhaps is ordered by acustomer that the producer does not have in sufficient quantity to meetthe customer's demands. Essentially, upon accepting a requiredspecification range set by a customer's intended use, a replacementasphaltic substance may be used to meet the customer's demands upon useof the present invention's accurate Heithaus parameter determinationcapability. A mix ratio may be determined according to the customer'sorder and the amounts of different types of asphalt available. This mixratio may then be used to create a sample for which an accurate Heithausparameter determination, and thus an accurate compatibility measurementis possible.

[0220] As can be easily understood from the foregoing, the basicconcepts of the present invention may be embodied in a variety of ways.It involves both analysis techniques as well as devices to accomplishthe appropriate analysis. In this application, the analysis techniquesare disclosed as part of the results shown to be achieved by the variousdevices described and as steps which are inherent to utilization. Theyare simply the natural result of utilizing the devices as intended anddescribed. In addition, while some devices are disclosed, it should beunderstood that these not only accomplish certain methods but also canbe varied in a number of ways. Importantly, as to all of the foregoing,all of these facets should be understood to be encompassed by thisdisclosure.

[0221] The discussion included in this application is intended to serveas a basic description. The reader should be aware that the specificdiscussion may not explicitly describe all embodiments possible; manyalternatives are implicit. It also may not fully explain the genericnature of the invention and may not explicitly show how each feature orelement can actually be representative of a broader function or of agreat variety of alternative or equivalent elements. Again, these areimplicitly included in this disclosure. Where the invention is describedin device-oriented terminology, each element of the device implicitlyperforms a function. Apparatus claims may not only be included for thedevice described, but also method or process claims may be included toaddress the functions the invention and each element performs. Neitherthe description nor the terminology is intended to limit the scope ofthe claims herein included.

[0222] It should also be understood that a variety of changes may bemade without departing from the essence of the invention. Such changesare also implicitly included in the description. They still fall withinthe scope of this invention. A broad disclosure encompassing both theexplicit embodiment(s) shown, the great variety of implicit alternativeembodiments, and the broad methods or processes and the like areencompassed by this disclosure and may be relied for support of theclaims of this application. It should be understood that any suchlanguage changes and broad claiming is herein accomplished. This fullpatent application is designed to support a patent covering numerousaspects of the invention both independently and as an overall system.

[0223] Further, each of the various elements of the invention and claimsmay also be achieved in a variety of manners. This disclosure should beunderstood to encompass each such variation, be it a variation of anembodiment of any apparatus embodiment, a method or process embodiment,or even merely a variation of any element of these. Particularly, itshould be understood that as the disclosure relates to elements of theinvention, the words for each element may be expressed by equivalentapparatus terms or method terms—even if only the function or result isthe same. Such equivalent, broader, or even more generic terms should beconsidered to be encompassed in the description of each element oraction. Such terms can be substituted where desired to make explicit theimplicitly broad coverage to which this invention is entitled. As butone example, it should be understood that all actions may be expressedas a means for taking that action or as an element which causes thataction. Similarly, each physical element disclosed should be understoodto encompass a disclosure of the action which that physical elementfacilitates. Regarding this last aspect, as but one example, thedisclosure of a “pump” should be understood to encompass disclosure ofthe act of “pumping”—whether explicitly discussed or not—and,conversely, were there effectively disclosure of the act of “pumping”,such a disclosure should be understood to encompass disclosure of a“pump” and even a “means for pumping.” Such changes and alternativeterms are to be understood to be explicitly included in the description.

[0224] Any patents, publications, or other references mentioned in thisapplication for patent are hereby incorporated by reference. Inaddition, as to each term used it should be understood that unless itsutilization in this application is inconsistent with suchinterpretation, common dictionary definitions should be understood asincorporated for each term and all definitions, alternative terms, andsynonyms such as contained in the Random House Webster's UnabridgedDictionary, second edition are hereby incorporated by reference.Finally, all references listed in the list of References To BeIncorporated By Reference In Accordance With The Patent Application orother information statement filed with the application are herebyappended and hereby incorporated by reference, however, as to each ofthe above, to the extent that such information or statementsincorporated by reference might be considered inconsistent with thepatenting of this/these invention(s) such statements are expressly notto be considered as made by the applicant(s).

[0225] Thus, the applicant(s) should be understood to claim at least: i)each of the analysis devices as herein disclosed and described, ii) therelated methods disclosed and described, iii) similar, equivalent, andeven implicit variations of each of these devices and methods, iv) thosealternative designs which accomplish each of the functions shown as aredisclosed and described, v) those alternative designs and methods whichaccomplish each of the functions shown as are implicit to accomplishthat which is disclosed and described, vi) each feature, component, andstep shown as separate and independent inventions, vii) the applicationsenhanced by the various systems or components disclosed, viii) theresulting products produced by such systems or components, ix) methodsand apparatuses substantially as described hereinbefore and withreference to any of the accompanying examples, x) the variouscombinations and permutations of each of the previous elementsdisclosed, xi) processes performed with the aid of or on a computer asdescribed throughout the above discussion, xii) a programmable apparatusas described throughout the above discussion, xiii) a computer readablememory encoded with data to direct a computer comprising means orelements which function as described throughout the above discussion,xiv) a computer configured as herein disclosed and described, xv)individual or combined subroutines and programs as herein disclosed anddescribed, xvi) the related methods disclosed and described, xvii)similar, equivalent, and even implicit variations of each of thesesystems and methods, xviii) those alternative designs which accomplisheach of the functions shown as are disclosed and described, xix) thosealternative designs and methods which accomplish each of the functionsshown as are implicit to accomplish that which is disclosed anddescribed, xx) each feature, component, and step shown as separate andindependent inventions, xxi) the various combinations and permutationsof each of the above, and xxii) each potentially dependent claim orconcept as a dependency on each and every one of the independent claimsor concepts presented. In this regard it should be understood that forpractical reasons and so as to avoid adding potentially hundreds ofclaims, the applicant may eventually present claims with initialdependencies only. Support should be understood to exist to the degreerequired under new matter laws—including but not limited to EuropeanPatent Convention Article 123(2) and United States Patent Law 35 USC 132or other such laws—to permit the addition of any of the variousdependencies or other elements presented under one independent claim orconcept as dependencies or elements under any other independent claim orconcept.

[0226] Further, if or when used, the use of the transitional phrase“comprising” is used to maintain the “open-end” claims herein, accordingto traditional claim interpretation. Thus, unless the context requiresotherwise, it should be understood that the term “comprise” orvariations such as “comprises” or “comprising”, are intended to implythe inclusion of a stated element or step or group of elements or stepsbut not the exclusion of any other element or step or group of elementsor steps. Such terms should be interpreted in their most expansive formso as to afford the applicant the broadest coverage legally permissible.

[0227] The claims set forth in this specification are herebyincorporated by reference as part of this description of the invention,and the applicant expressly reserves the right to use all of or aportion of such incorporated content of such claims as additionaldescription to support any of or all of the claims or any element orcomponent thereof, and the applicant further expressly reserves theright to move any portion of or all of the incorporated content of suchclaims or any element or component thereof from the description into theclaims or vice-versa as necessary to define the matter for whichprotection is sought by this application or by any subsequentcontinuation, division, or continuation-in-part application thereof, orto obtain any benefit of, reduction in fees pursuant to, or to complywith the patent laws, rules, or regulations of any country or treaty,and such content incorporated by reference shall survive during theentire pendency of this application including any subsequentcontinuation, division, or continuation-in-part application thereof orany reissue or extension thereon.

LIST OF REFERENCES TO BE INCORPORATED BY REFERENCE IN ACCORDANCE WITHTHIS PATENT APPLICATION

[0228] LIST OF REFERENCES TO BE INCORPORATED BY REFERENCE IN ACCORDANCEWITH THIS PATENT APPLICATION “Annual Technical Report: Nov. 1, 1995-May15, 1996” Fundamental Properties of Asphalts and Modified Asphalts,Western Research Institute, pp. 303-331 (1996) “Final Report - NewMethods: Volume 2” Fundamental Properties of Asphalts and ModifiedAsphalts, Western Research Institute, pp. 303-331 (1998) “FundamentalProperties of Asphalts and Modified Asphalts, Volume 1, Final Report,New Method”, Federal Highway Administration, 245 pp., October 2001Heithaus, J. J., “Measurement and Significance of AsphaltenePeptization,” Symposium on Fundamental Nature of Asphalt PresentedBefore the Division of Petroleum Chemistry, American Chemical Society,New York Meeting Sep. 11-16, (1960) 8 pp. Heithaus, J. J., “Measurementand Significance of Asphaltene Peptization,” Journal of the Institute ofPetroleum, Vol. 48, No. 458, pp. 45-53 (1962) “Interpretive FinalReport: Draft: Volume 1” Fundamental Properperties of Asphalts andModified Asphalts, Western Research Institute, pp. 303-331 (1997) Pauli,A., “Asphalt Compatibility Testing Using the Automated HeithausTitration Test,” Western Research Institute, pp. 1276-1231 (1996) Pauli,A., “Rheological and Compositional definitions of Compatibility as theyRelate to the Colloidal Model of Asphalt and Residual;” Symposium onStability and Compatibility of Fuel Oils and Heavy Ends Presented Beforethe Division of Petroleum Chemistry, Inc., 217th National Meeting,American Chemical Society, Mar. 21-25, 1999, pp. 190-193. Pauli, A. andBranthaver, J., “Relationships Between Asphaltenes, HeithausCompatibility Parameters, and Asphalt Viscosity, “Petroleum Science andTechnology, 16 (9&10), pp. 1125-1147 (1998) PCT applicationWRI-CokeIndex-PCT/US00/15950, filed Oct. 27, 2000, entitled “PredictingProximity to Coke Formation” Reichert, et al., “Measurement ofasphaltene flocculation in bitumen solutions”, The Journal of CanadianPetroleaum Techonology, Sep-Oct 1986 Montreal, pp. 33-37 “QuarterlyTechnical Report: Aug. 16-Nov. 15, 1999 “Western Research Institute, pp.177-197 (1999) “Quarterly Technical Report: Nov. 16, 1999-Feb. 15, 2000”Western Research Institute, pp. 159-174 (2000) “Quarterly TechnicalReport: May 16-Aug. 15, 1999” Western Research Institute, pp. 159-165(1999) Redelius, P.G., “Solubility Parameters and Bitumen,” Fuel 79, pp.27-35, (2000) “Standard Method for Automated Heithaus Titrimetry”, ASTMMeeting, August 2000, pp. 1-13 Schabron, J. and Pauli, A., “CokingIndexes Using The Heithaus titration and Asphaltene Solubility,”Symposium on Stability and Compatibility of Fuel Oils and Heavy EndsPresented Before the Division of Petroleum Chemistry, Inc., 217thNational Meeting, American Chemical Society, Mar. 21-25, 1999, pp. 187-189 US National Phase Application, 10/009,863, entitled “PredictingProximity to Coke Formation,”filed Dec. 12, 2001 US Provisional PatentApplication, 60/138,846, entitled “Predicting Proximity to CokeFormation,” filed Jun. 10, 1999

What is claimed is:
 1. A titration method comprising the steps of: a.creating a solution by dissolving at least one soluble substance in asolvent; b. establishing said solution in a solution containmentelement; c. excluding gas from said solution; d. monitoring a parameterof said solution d. controllably adding a titrant to said solution; e.achieving a threshold solution change; and f. determining at least oneHeithaus parameter. 2 A titration method as in claim 1 wherein said stepof monitoring a parameter of said solution comprises the step ofspectrophotometrically monitoring said solution.
 3. A titration methodas in claim 2 wherein said step of spectrophotometrically monitoringsaid solution comprises the step of monitoring solution turbidity.
 4. Atitration method as in claim 1 further comprising the step ofcirculating said solution through a solution circulation system.
 5. Atitration method as in claim 1 further comprising the steps of a.altering a character of said solution to eliminate said thresholdsolution change after said step of achieving a threshold solutionchange; b. achieving at least a second threshold solution change; and c.determining a characteristic of at least one substance of said solutionas a result of said step of achieving at least one of said thresholdsolution changes.
 6. A titration method as in claim 2 further comprisingthe step of circulating said solution through a solution circulationsystem.
 7. A titration method as in claim 1 wherein said step ofdetermining at least one Heithaus parameter comprises the step ofautomatically determining said at least one Heithaus parameter using acomputer program.
 8. A titration method as in claim 2 wherein said stepof determining at least one Heithaus parameter comprises the step ofautomatically determining said at least one Heithaus parameter using acomputer program.
 9. A titration method as in claim 4 wherein said stepof determining at least one Heithaus parameter comprises the step ofautomatically determining said at least one Heithaus parameter using acomputer program.
 10. A titration method as in claim 6 wherein said stepof determining at least one Heithaus parameter comprises the step ofautomatically determining said at least one Heithaus parameter using acomputer program.
 11. A titration method as in any of claims 1, 2, 3, 4,5, 6, 7, 8, 9, or 10 further comprising a temperature maintenanceelement to which said solution is responsive.
 12. A titration apparatuscomprising: a. a titrant containment element; b. a titrant deliveryelement responsive to said titrant containment element; c. a solutioncontainment element fluidicly responsive to said titrant containmentelement; d. a solution circulation system responsive to said solutioncontainment element; and e. a spectrophotometer responsive to saidsolution circulation system.
 13. A titration apparatus as in claim 12wherein said solution circulation system comprises a low volume solutioncirculation system.
 14. A titration apparatus as in claim 12 furthercomprising a gas exclusion element within which said titrant deliveryelement is operable.
 15. A titration apparatus as in claim 13 furthercomprising a gas exclusion element within which said titrant deliveryelement is operable.
 16. A titration apparatus as in claim 12 furthercomprising a computerized threshold change indicator which is configuredto respond to a solution contained within said solution containmentelement.
 17. A titration apparatus as in claim 13 further comprising acomputerized threshold change indicator which is configured to respondto a solution contained within said solution containment element.
 18. Atitration apparatus as in claim 14 further comprising a computerizedthreshold change indicator which is configured to respond to a solutioncontained within said solution containment element.
 19. A titrationapparatus as in claim 15 further comprising a computerized thresholdchange indicator which is configured to respond to a solution containedwithin said solution containment element.
 20. A titration apparatus asin any of the claims 12, 13, 14, 15, 16, 17, 18, or 19 furthercomprising a solution temperature maintenance element to which saidsolution is responsive.
 21. A titration method comprising the steps of:a. creating a solution by dissolving at least one soluble substance in asolvent; b. establishing said solution within a solution containmentelement; c. controllably adding a titrant to said solution within saidsolution containment element; d. achieving a first threshold solutionchange as a result of said step of controllably adding a titrant to saidsolution; e. altering a character of said solution to eliminate saidfirst threshold solution change; f achieving at least a second thresholdsolution change; and g. determining a characteristic of at least onesubstance of said solution as a result of said step of achieving atleast one of said threshold solution changes.
 22. A titration method asdescribed in claim 21 wherein said step of achieving at least a secondthreshold solution change comprises the step of controllably addingadditional titrant to said solution within said solution containmentelement.
 23. A titration method as described in claim 22 wherein saidstep of altering a character of said solution to eliminate said firstthreshold solution change comprises the step of adding a solvent to saidsolution.
 24. A titration method as described in claim 23 and furthercomprising the step of repetitively achieving additional thresholdsolution changes prior to accomplishing said step of determining acharacteristic of at least one substance of said solution.
 25. Atitration method as described in claim 21 and further comprising thestep of maintaining said solution at a desired temperature whileachieving said threshold solution changes.
 26. A titration method asdescribed in claim 21 and further comprising the step of excluding gasfrom said solution.
 27. A titration method as described in claim 21wherein said step of determining a characteristic of at least onesubstance of said solution comprises the step of spectrophotometricallyanalyzing said solution.
 28. A titration method as described in claim 21and further comprising the step of monitoring a solution change index atthe time of accomplishing said steps of achieving said thresholdsolution changes.
 29. A titration method as described in claim 28wherein said step of monitoring a solution change index comprises thestep of monitoring solution turbidity.
 30. A titration method asdescribed in claim 29 wherein said step of monitoring solution turbiditycomprises the step of spectrophotometrically analyzing said solution.31. A titration method as described in claim 21 wherein said steps ofachieving said threshold solution changes comprise the step of causing aflocculation onset.
 32. A titration method as described in claim 21 andfurther comprising the step of preliminarily assessing a parameter ofsaid solution after accomplishing said step of achieving a firstthreshold solution change as a result of said step of controllablyadding a titrant to said solution.
 33. A titration method as describedin claim 21 wherein said step of controllably adding a titrant to saidsolution within said solution containment element comprises the step ofcontinuously adding a titrant to said solution within said solutioncontainment element.
 34. A titration method as described in claim 21wherein said step of altering a character of said solution to eliminatesaid first threshold solution change comprises the step of achieving alower solubility parameter for said solution.
 35. A titration method asdescribed in claim 21 wherein said step of creating a solution bydissolving at least one soluble substance in a solvent comprises thestep of mixing a petroleum residua with a solvent.
 36. A titrationmethod as described in claim 35 wherein said step of controllably addinga titrant to said solution within said solution containment elementcomprises the step of controllably adding a titrant selected from agroup consisting of: aliphatic hydrocarbon substances and alcoholsubstances.
 37. A titration method as described in claim 36 wherein saidstep of mixing a petroleum residua with a solvent comprises the step ofmixing a petroleum residua with a solvent selected from a groupconsisting of: toluene and benzene.
 38. A titration apparatuscomprising: a. a titrant containment element; b. a titrant deliveryelement responsive to said titrant containment element; c. a solutioncontainment element capable of containing a solution and fluidiclyresponsive to said titrant containment element; d. a solution thresholdchange detector configured to respond to a solution contained withinsaid solution containment element; and e. a solution characteralteration element responsive to said solution threshold changedetector.
 39. titration apparatus as described in claim 38 wherein saidsolution character alteration element comprises a metered solventaddition system.
 40. A titration apparatus as described in claim 39wherein said solution threshold change detector comprises a repetitivesolution threshold change detector.
 41. A titration apparatus asdescribed in claim 38 further comprising a temperature control elementto which said solution containment element is responsive.
 42. Atitration apparatus as described in claim 38 and further comprising agas exclusion element within which said titrant delivery element isoperable.
 43. A titration apparatus as described in claim 38 and whreinsaid solution threshold change dector compriese an automatic solutioncharacter determination element.
 44. A titration apparatus as describedin claim 43 wherein said automatic solution character determinationelement comprises a spectrophotometer.
 45. A titration apparatus asdescribed in claim 43 wherein said automatic solution characterdetermination element comprises a solution change index monitor.
 46. Atitration apparatus as described in claim 45 wherein said solutionchange index monitor comprises a solution turbidity monitor.
 47. Atitration apparatus as described in claim 46 wherein said solutionturbidity monitor comprises a spectrophotometer.
 48. A titrationapparatus as described in claim 38 wherein said solution thresholdchange detector comprises a flocculation onset monitor.
 49. A titrationapparatus as described in claim 38 wherein said titrant delivery elementcomprises a continuous titrant delivery element.
 50. A titrationapparatus as described in claim 39 wherein said titrant delivery elementis selected from a group consisting of: an aliphatic hydrocarbonsubstance delivery element and alcohol substance delivery element.
 51. Atitration apparatus as described in claim 50 wherein said meteredsolvent addition system is selected from a group consisting of: meteredtoluene addition element and a metered benzene addition element.
 52. Atitration method comprising the steps of: a. creating a solution bydissolving at least one soluble substance in a solvent; b. establishingsaid solution within a solution containment element; c. controllablyadding a titrant to said solution within said solution containmentelement while accomplishing the step of; d. excluding gas from saidsolution; e. monitoring a parameter of said solution while accomplishingsaid step of controllably adding said titrant to said solution; f.achieving a threshold solution change while accomplishing said step ofmonitoring said parameter of said solution; and g. determining acharacteristic of at least one substance of said solution as a result ofsaid step of achieving a threshold solution change.
 53. A titrationmethod as described in claim 52 wherein said step of controllably addinga titrant to said solution within said solution containment elementcomprises the step of continually adding a titrant to said solutionwithin said solution containment element.
 54. A titration method asdescribed in claim 52 wherein said step of determining a characteristicof at least one substance of said solution comprises the step ofdetermining at least one Heithaus parameter.
 55. A titration method asdescribed in claim 52 wherein said step of controllably adding a titrantto said solution within said solution containment element comprises thestep of adding said titrant at an optimal solubility reduction responserate.
 56. A titration method as described in claim 52 further comprisingthe step of maintaining said solution at a desired temperature.
 57. Atitration method as described in claim 52 wherein said step of excludinggas from said solution comprises the step of hermetically sealing.
 58. Atitration method as described in claim 52 wherein said step of monitor aparameter of said solution comprises the step of spectrophotometricallymonitoring.
 59. A titration method as described in claim 52 wherein saidstep of achieving a threshold solution change comprises the step ofachieving onset of flocculation.
 60. A titration method as described inclaim 52 wherein said step of creating a solution comprises the step ofmixing a petrol residua with said solvent.
 61. A titration method asdescribed in claim 60 wherein said step of mixing a petroleum residuawith said solvent comprises the step of mixing said petroleum residuawith a solvent selected from the group consisting of: toluene andbenzene.
 62. A titration method as described in claim 52 wherein saidstep of controllably adding a titrant to said solution within saidsolution containment element comprises the step of continually adding atitrant selected from the group consisting of: aliphatic hydrocarbonsand alcohol substances.
 63. A titration method as described in claim 52wherein said step of monitoring a parameter of said solution comprisesthe step of monitoring solution turbidity.
 64. A titration method asdescribed in claim 63 wherin said step of monitor solution turbiditycomprises the step of spectrophotometrically monitoring.
 65. A titrationmethod as described in claim 52 wherein said step of monitor a parameterof said solution comprises the step of circulating said solution througha solution circulation system.
 66. A titration method as described inclaim 65 wherein said step of circulating said solution through asolution circulation system comprises the step of circulating saidsolution through a flow cell element.
 67. A titration method asdescribed in claim 65 wherein said step circulating said solutionthrough a solution circulation system comprises circulating less than10% of an initial solution volume.
 68. A titration method as describedin claim 52 wherein said step of monitoring a parameter of said solutioncomprises the step of circulating said solution through a low volumesolution circulation system.
 69. A titration method as described inclaim 58 wherein said step of spectrophotometricaly monitoring comprisesthe step of config a spectrophotometer to detect change in lighttransmittance through said solution.
 70. A titration method as describedin claim 57 wherein said step of hermetically sealing comprises the stepof hermetically sealing said solution containment element.
 71. Atitration method as described in claim 70 wherein said step ofhermetically sealing said solution containment element comprises thestep of sealing with a Teflon® lined cap.
 72. A titration method asdescribed in claim 70 wherein said step of hermetically sealing furthercomprises the step of hermetically sealing a titrant containmentelement.
 73. A titration method as described in claim 56 wherein saidstep of maintaining said solution at a desired temperature comprises thestep of operating a joined heat transfer system.
 74. A titration methodas described in claim 56 wherein said step of maintaining a solution ata desired temperature comprises the step of pumping a fluid.
 75. Atitration method as described in claim 73 wherein said step of operatinga joined heat transfer system comprises the step of pumping a fluid. 76.A titration method as described in claim 52 wherein said step ofmonitoring a parameter comprises the step of electronic monitoring. 77.A titration method as described in claim 76 wherein said step ofelectronic monitoring comprises the step of computerized monitoring. 78.A titration method as described in claim 54 wherein said step ofdetermining at least one Heithaus parameter comprises the step ofautomatically determining at least one Heithaus parameter using acomputer program.
 79. A titration method as described in either claim 52or 78 wherein said step of monitoring a parameter of said solutoncomprises the step of automatically activating electronic components.80. A titration method as described in claim 65 wherein said step ofcirculating said solution through a solution circulation systemcomprises the step of pumping said solution.
 81. A titration method asdescribed in either claim 52 or 80 wherein said step of controllablyadding a titrant comprises the step of pumping.
 82. A titration methodas described in claim 65 wherein said step of circulating said solutionthrough a solution circulation system comprises the step of circulatingsaid solution through tubing having a reduced flow resistance internalsurface.
 83. A titration method as described in claim 52 wherein saidstep of determining a characteristic of at least one substance of saidsolution comprises the step of ascertaining an added titrant amount. 84.A titration method as described in claim 57 wherein said step ofexcluding gas from said solution further comprises the step ofpressurizedly purging substantially all oxygen from said solutioncontainment element.
 85. A titration method as described in claim 52wherein said step of controllably adding a titrant to said solutioncomprises the step of continually adding said titrant to said solution.86. A titration method as described in claim 85 wherein said step ofcontinaully adding said titrant to said solution comprises the step ofcontinually adding said titrant at an optimal solubility reductionresponse rate.
 87. A titration apparatus comprising: a. a titrantcontainment element; b. a titrant delivery element responsive to saidtitrant containment element; c. a solution containment element fluidiclyresponsive to said titrant containment element; and d. a gas exclusionelement within which said titrant delivery element is operable. 88 Atitration apparatus as described in claim 87 and further comprising asolution change detection element which is configured to respond to asolution contained within said solution containment element.
 89. Atitration apparatus as described in claim 88 and further comprising asolution circulation system responsive to said solution containmentelement.
 90. A titration apparatus as described in claim 88 wherein saidsolution change detection element comprises a flocculation onsetdetection element.
 91. A titration apparatus as described in claim 88wherein said solution change detection element comprises aspectrophotometer.
 92. A titration apparatus as described in claim 89wherein said solution circulation system comprises a flow cell element.93. A titration apparatus as described in claim 92 wherein said solutionchange detection element is responsive to said flow cell element.
 94. Atitration apparatus as described in claim 93 wherein said solutionchange detection element comprises a spectrophotometer.
 95. A titrationapparatus as described in claim 94 wherein said spectrophotometercomprises a spectrophotometer configured to detect change in lighttransmittance.
 96. A titration apparatus as described in claim 89wherein said solution circulation system comprises a low volume solutioncirculation system.
 97. A titration apparatus as described in claim 96wherein said low volume solution circulation system has a volume of notmore than about ten per-cent of an initial solution volume before anyaddition of titrant.
 98. A titration apparatus as described in claim 91,94, or 95 wherein said solution circulation system comprises a lowvolume solution circulation system.
 99. A titration apparatus asdescribed in claim 98 wherein said low volume solution circulationsystem has a volume of not more than about ten per-cent of an initialsolution volume before any addition of titrant.
 100. A titrationapparatus as described in claim 87 wherein said gas exclusion elementcomprises at least one hermetic seal.
 101. A titration apparatus asdescribed in claim 100 wherein said at least one hermetic seal comprisesa solution containment element hermetic seal.
 102. A titration apparatusas described in claim 101 wherein said solution containment elementhermetic seal comprises a solution-titrant compatible tight fittingtitration test container cap.
 103. A titration apparatus as described inclaim 102 wherein said solution-titrant compatible tight fittingtitration test container cap comprises a Teflon® lined solutioncontainment element cap.
 104. A titration apparatus as described inclaim 101 wherein said at least one hermetic seal comprises a titrantcontainment element hermetic seal.
 105. A titration apparatus asdescribed in claim 100 wherein said at least one hermetic sealcomprises: a. a solution containment element hermetic seal; and b. atitrant containment element hermetic seal.
 106. A titration apparatus asdescribed in claim 87 wherein said titrant delivery element comprises ahermetically sealed titrant delivery element.
 107. A titration apparatusas described in claim 87 or 94 and further comprising a temperaturemaintenance element to which said solution containment element isresponsive.
 108. A titration apparatus as described in claim 107 whereinsaid temperature maintenance element to which said solution containmentelement is responsive comprises a solution containment element heattransfer element.
 109. A titration apparatus as described in claim 107wherein said temperature maintenance element to which said solutioncontainment element is responsive comprises a titrant containmentelement heat transfer element.
 110. A titration apparatus as describedin claim 108 wherein said temperature maintenance element to which saidsolution containment element is responsive further comprises a titrantcontainment element heat transfer element.
 111. A titration apparatus asdescribed in claim 110 wherein said solution containment element heattransfer element and said titrant containment element heat transferelement comprise a joined heat transfer system.
 112. A titrationapparatus as described in claim 108 or 111 wherein said solutioncontainment element heat transfer element comprise a fluid pump.
 113. Atitration apparatus as described in claim 88, 89, 90, 91, 92, 95, or 97and further comprising a threshold change indicator which is responsiveto said solution containment element.
 114. A titration apparatus asdescribed in claim 113 wherein said threshold change indicator comprisesa light transmittance threshold change indicator.
 115. A titrationapparatus as described in claim 114 and further comprising a systemactivation element responsive to said light transmittance thresholdchange indicator.
 116. A titration apparatus as described in claim 87,89, 91, 94, or 95 and further comprising a solvent introduction systemto which said solution containment element is responsive.
 117. Atitration apparatus as described in claim 87, 89, 91, 94, or 95 andfurther comprising an automatic solvent introduction system to whichsaid solution containment element is responsive.
 118. A titrationapparatus as described in claim 115 and further comprising and furthercomprising a solvent introduction system responsive to said systemactivation element.
 119. A titration apparatus as described in claim 87wherein said titrant delivery element comprises a titrant pump.
 120. Atitration apparatus as described in claim 89 or 97 wherein said solutioncirculation system comprises a solution pump.
 121. A titration apparatusas described in claim 119 wherein said solution circulation systemcomprises a solution pump.
 122. A titration apparatus as described inclaim 119 wherein said titrant delivery element comprises internallyTeflon® coated conduit.
 123. A titration apparatus as described in claim120 wherein said solution circulation system comprises internallyTeflon® coated conduit.
 124. A titration apparatus as described in claim122 wherein said solution circulation system comprises internallyTeflon® coated conduit.
 125. A method of preparing a compatibleasphaltic composite comprising the steps of: a. obtaining a first typeof asphalt substance; b. obtaining at least a second type of asphaltsubstance; c. affirmatively and accurately determining an optimalasphalt mix ratio between said first type of asphalt substance with atleast said second type of asphalt substance; and d. mixing a quantity ofsaid first type of asphalt substance with a quantity of said second typeof asphalt substance in accordance with said optimal asphalt mix ratioto produce a commercial quantities of a compatible asphaltic composite.126. A method of preparing a compatible asphaltic composite as describedin claim 125 wherein said step of affirmatively and accuratelydetermining an optimal asphalt mix ratio between said first type ofasphalt substance with at least said second type of asphalt substancecomprises the step of mixing said first type of asphalt substance withat least said second type of asphalt substance to at least onepredetermined ratio to create at least one intermediate asphalticcomposite.
 127. A method of preparing a compatible asphaltic compositeas described in claim 126 wherein said step of affirmatively andaccurately determining an optimal asphalt mix ratio between said firsttype of asphalt substance with at least said second type of asphaltsubstance further comprises the step of accurately determining the longterm compatibility of said at least one intermediate asphalticcomposite.
 128. A method of preparing a compatible asphaltic compositeas described in claim 126 wherein said step of affirmatively andaccurately determining an optimal asphalt mix ratio between said firsttype of asphalt substance with at least said second type of asphaltsubstance further comprises the step of mixing said first type ofasphalt substance with at least said second type of asphalt substance toat least one additional predetermined ratio to create at least oneadditional intermediate asphaltic composite.
 129. A method of preparinga compatible asphaltic composite as described in claim 128 wherein saidstep of affirmatively and accurately determining an optimal asphalt mixratio between said first type of asphalt substance with at least saidsecond type of asphalt substance further comprises the step ofaccurately determining the long term compatibility of said at least oneadditional intermediate asphaltic composite.
 130. A method of preparinga compatible asphaltic composite as described in claim 129 wherein saidstep of affirmatively and accurately determining an optimal asphalt mixratio between said first type of asphalt substance with at least saidsecond type of asphalt substance further comprises the step ofaccurately determining a first set of Heithaus parameters for saidintermediate asphaltic composite.
 131. A method of preparing acompatible asphaltic composite as described in claim 130 wherein saidstep of affirmatively and accurately determining an optimal asphalt mixratio between said first type of asphalt substance with at least saidsecond type of asphalt substance further comprises the step ofaccurately determining an additional set of Heithaus parameters for atleast one additional intermediate asphaltic composite.
 132. A method ofpreparing a compatible asphaltic composite as described in claim 131wherein said step of affirmatively and accurately determining an optimalasphalt mix ratio between said first type of asphalt substance with atleast said second type of asphalt substance further comprises the stepof accurately generating a first compatibility measurement of at leastone intermediate asphaltic composite.
 133. A method of preparing acompatible asphaltic composite as described in claim 132 wherein saidstep of affirmatively and accurately determining an optimal asphalt mixratio between said first type of asphalt substance with at least saidsecond type of asphalt substance further comprises the step ofaccurately generating at least one additional compatibility measurementof at least one additional intermediate asphaltic composite.
 134. Amethod of preparing a compatible asphaltic composite as described inclaim 133 wherein said step of affirmatively and accurately determiningan optimal asphalt mix ratio between said first type of asphaltsubstance with at least said second type of asphalt substance furthercomprises the steps of: a. comparing a plurality of compatibilitymeasurements of intermediate asphaltic composites; and b. selecting anoptimal asphalt mix ratio based upon said plurality of compatibilitymeasurements.
 135. A method of preparing a compatible asphalticcomposite as described in claim 134 wherein said step of mixing aquantity of said first type of asphalt substance with a quantity saidsecond type of asphalt substance in accordance with said optimal asphaltmix ratio to producing a commercial quantities of a compatible asphalticcomposite comprises the step of mixing a tonnage amount of said firsttype of asphalt substance with a tonnage amount of said second type ofasphalt substance in accordance with said optimal asphalt mix ratio toproducing a commercial quantities of a compatible asphaltic composite.136. A compatible blended asphalt product comprising: a. a commercialquantity of a first superior character asphalt substance; and b. acommercial quantity of maximal blend ratio of at least a second inferiorcharacter asphalt substance.
 137. A method of preparing a compatibleasphaltic composite comprising the steps of: a. obtaining a first typeof asphalt substance; b. obtaining at least a second type of asphaltsubstance; c. mixing a quantity of said first type of asphalt substancewith a quantity said second type of asphalt substance to create anintermediate asphaltic composite with a predetermined ratio; and d.accurately generating a compatibility measurement of said intermediateasphaltic composite.
 138. A method of preparing a compatible asphalticcomposite as described in claim 137 wherein said second type of asphaltsubstance comprises a replacement asphaltic substance, and furthercomprising the steps of: a. accepting a required specification range fora character of an asphaltic composite; and b. determining a mix ratio toproduce an asphaltic composite within said required specification range;and c. mixing a quantity of said first type of asphalt substance with aquantity said replacement asphalt substance to said mix ratio to createan asphaltic composite within said required specification range.
 139. Acompatible asphaltic composite produced according to any of theaforementioned steps.
 140. A titration apparatus comprising: a. atitrant containment element; b. a titrant delivery element responsive tosaid titrant containment element; c. a composite asphalt containmentelement capable of containing a composite asphalt substance composed atleast of a first type of asphalt substance and a second type of asphaltsubstance and fluidicly responsive to said titrant containment element;and d. an optimal mix ratio determination system configured to respondto a composite asphalt substance contained within said composite asphaltcontainment element.
 141. A titration apparatus as described in claim140 wherein said optimal mix ratio determination system comprises aspectrophotometer.
 142. A titration apparatus as described in claim 140and further comprising multiple composite asphalt containment elements.143. A titration apparatus as described in claim 142 wherein saidoptimal mix ratio determination system comprises multiple solutioncharacter determination elements.
 144. A titration apparatus asdescribed in claim 143 wherein said optimal mix ratio determinationsystem further comprises a long term compatability determinationelement.
 145. A titration apparatus as described in claim 142 whereinsaid optimal mix ratio determination system comprises a Heithausparameter determination element.
 146. A titration apparatus as describedin claim 145 wherein said Heithaus parameter determination elementcomprises a multiple Heithaus parameter determination element.